Alkyl arylsulfonate exchange process

ABSTRACT

A process for exchanging alkyl moieties between compounds comprising reacting a lower alkyl arylsulfonate with a higher alkyl halide in the presence of an organic quaternary salt. The process is useful in converting the higher alkyl group of the starting halide to the corresponding alcohols by first employing the process of the invention to convert the higher alkyl group to the corresponding arylsulfonate followed by hydrolysis to produce the higher alkanols.

United States Patent [1 1 Starks et al.

[ Oct. 21, 1975 ALKYL ARYLSULFONATE EXCHANGE PROCESS [75] Inventors: Charles M. Starks, Ponca City,

Okla; Owen Portwood, Jr., Janesville, Wis.

[73] Assignee: Continental Oil Company, Ponca City, Okla.

[22] Filed: July 2, 1973 [21] Appl. No.: 371,230

[52] US. Cl 260/456 P; 260/652 R [51] Int. Cl. C07C 143/68 [58] Field of Search 260/456 P, 456 R [56] References Cited OTHER PUBLICATIONS l-loffmann, J. Chem. Soc., 1965, pp. 6753-6769.

Primary Examiner-Bemard Helfin Assistant ExaminerNicky Chan' Attorney, Agent, or Firm-Cortlah R. Schupbach, Jr.

[5 7 ABSTRACT A process for exchanging alkyl moieties between com- 7 Claims, No Drawings ALKYL ARYLSULFONATE EXCHANGE PROCESS This invention relates to an alkyl exchange process which has utility in an overall scheme for producing alkanols.

Briefly described, the invention involves a process wherein the alkyl group of a higher alkyl halide is exchanged with the alkyl group of a lower alkyl arylsulfonate in the presence of an organic quaternary salt. The resulting higher alkyl arylsulfonate product may then be easily hydrolyzed to produce the corresponding higher alkanols.

The higher alkyl halide which may be used in the invention are described by the formula RX wherein R is a straight or branch chain alkyl having from 6 to 40 carbon atoms and x is a halogen such as bromine, chlorine or iodine. These halides are readily obtained by reacting olefins having 6 to 40 carbon atoms with a hydrogen halide such as l-lBr or HCl as is known in the art.

Illustrative of suitable alkyl halides described above are hexyl chloride, nonyl chloride, decyl bromide, eicosyl chloride, l-metehylheptadecyl bromide, tetradecyl chloride, nonyl iodide, octyl bromide, 2-ethylhexy1 chloride, nonacosyl bromide, 2-octyldecyl chloride, Z-tetradecylhexadecyl bromide, and the like.

The lower alkyl arylsulfonates which are reacted with the above alkyl halides in the exchange process are defined by wherein n is zero or one; R is a halogen, such as bromine or chlorine, or a C to C alkyl group; and R is a C, to C alkyl group. These compounds are readily obtained by reaction of C to C lower alkanols with the corresponding arylsulfonyl chloride or arylsulfonic acid.

Illustrative of the lower alkyl arylsulfonates include methyl p-methylbenzene sulfonate, methyl pbromobenzene sulfonate, ethylbenzene sulfonate, butylbenzene sulfonate, propylchlorobenzene sulfonate, ethyl p-methylbenzene sulfonate, ethyl butylbenzene sulfonate, and the like.

The exchange reaction between the above-described reactants is carried out in the presence of an organic quaternary salt such as are described in British Pat. No. 1,227,144. Generally, these salts may be defined by the formula wherein M is a pentavalent ion of an element selected from the group consisting of nitrogen, phosphorus, arsenic, antimony and bismuth; each of R R R and R is, independently, an alkyl group containing 1 to 30 carbon atoms, a phenyl group, a benzyl group, or an alkyl substituted benzyl group wherein the alkyl group has 1 to 30 carbon atoms; and X is hydroxide or an anion derived from an organic or inorganic acid such as a halide, e.g., bromine or chlorine, sulfate, sulfonate, or acetate. Preferably, M is nitrogen, phosphorous or arsenic; each of R R R and R are alkyl groups; and X is a halide.

Some examples of these quaternary salts include hexadecyltrihexylammonium bromide, didodecyldimethylammonium chloride, tetraheptylammonium iodide, trioctylethylammoniumbromide, tetranonylammonium hydroxide, tricaprylyldodecylammonium ptoluene sulfonate, tributyldecylphosphonium bromide, tetradodecylphosphonium chloride, triphenyldecylphosphonium chloride, trioctylbenzylammonium bromide, tributyloctadecylphosphonium bromide, tribenzyldecylarsonium chloride, and

The exchange process is carried out by bringing together the higher alkyl halide and the lower alkyl arylsulfonate, such as in a reaction vessel, in the presence of the organic quaternary salt. The ratio of the higher alkyl halide to the sulfonate is not critical as the reaction is an equilibrium reaction and will proceed to some extent as long as some of each reactant is present. It is desirable, however, to operate with about a one-to-one molar ratio or with an excess of the sulfonate to drive the reaction toward completion with the greatest conversion of the alkyl halide as is desirable for an overall scheme in producing higher alkanols.

The organic quaternary salt should be employed in an amount of at least about 0.01 weight percent based on the total organic reactants, and preferably in an amount in the range of about 0.01 to 10 weight percent.

The temperatures employed in the exchange process can vary widely, depending on the desired reaction rates as well as the particular organic reactants and the organic quaternary salt. Generally, temperatures in the range of 0C to 200C may be employed. However, as previously indicated and as is understood in the art, the temperatures employed for any specific reaction must take into consideration the decomposition temperatures of the reactants as well as the quaternary salt.

The process is preferably carried out with the reactants in the liquid phase. Generally, the reactants are liquids at ambient conditions or may be rendered in the liquid phase under reaction conditions. In those instances where the desired reaction conditions are insufficient to render the reactants liquid, or where diluents may be desired, inert solvents may be employed. Such solvents are well-known to the art and include such things as hydrocarbons (e.g., benzene, toluene and paraffins), ethers, chloroform and other inert materials capable of dissolving the organic reactants.

The higher alkyl arylsulfonate product produced by the alkyl exchange process of this invention is readily hydrolyzed to convert the high alkyl moieties to the corresponding higher alkanols which have a variety of known uses, e.g., solvents, precursors for detergents,

etc.

The following examples will serve to further illustrate the invention.

EXAMPLE 1 To a ml Erlenmyer flask there were charged 0.1 mol ethylbenzene sulfonate, 0.1 mol n-octyl bromide and about 0.5 g tributylhexadecylammonium bromide. The flask was fitted with a condenser and stirrer. With stirring, the reaction mixture was heated to about 60C and maintained for 12 hours whereupon a sample was withdrawn and analyzed by gas chromatography. Analysis indicated that substantially equimolar amounts of ethylbenzene sulfonate, n-octylbenzene sulfonate, n-

ery of the desired product which is in a liquid state. This technique is particularly applicable to the general process wherein the lower alkyl arylsulfonates employed as reactants results in relatively highly volatile lower alkyl halides in the product mixture- EXAMPLE 2 Similar results as obtained in Example 1 using the same procedure may be produced by reacting eicosyl chloride and methyl p-bromobenzene sulfonate in the presence of tetranonylammonium hydroxide.

EXAMPLE 3 V Following Example 2, 2-ethylhexyl chloride and propylchlorobenzene sulfonate may be reacted in the presence of triphenyldecylphosphonium chloride to produce similar results.

EXAMPLE 4 l-methylheptadecyl chloride and ethyl pmethylbenzene sulfonate may be reacted in the presence 'of triberizyldecylarsonium chloride as described I in 'E'xam plej'to effect alkyl'exchange.

EXAMPLE 5 Alkyl exchange may be effected similarly as described in 'Example 2 by reacting decyl bromide with methylbe'nzene sulfonate in the presence of trioctylethylammonium bromide.

Thus having described the invention in detail, it will be understood by those skilled in the art that certain variations and modifications may be made without departing from the spirit and scope of the invention as described herein and in the appended claims.

We claim:

' l. A process for exchanging alkyl moieties between 7 compounds which comprises reacting a lower alkyl aryl :sulfonate with a higher alkyl halide at temperatures in :thexrangc of 0C to 200C in the presence of at least 0.01 weight percent of an organic quaternary salt based on the total alkyl halide and alkyl aryl sulfonate; said lower alkyl aryl sulfonate being defined by-the formula Rlln wherein n is zero or one; R is halogen or C to C alkyl group, and R" is a C and C alkyl group; said higher alkyl halide being defined by the formula RX wherein R is. a straight or branch chain alkyl grup having 6 to 40 carbon atoms and X is chlorine, bromine, or iodine; said alkyl moieties being exchanged being R and R;

and said organic quaternary salt being defined by the formula (R1R2R3R4M X wherein M is a pentavalent ion of an element selected from the group consisting of nitrogen and phosphorus; each of R R R and R independently, is an alkyl group having 1 to 30 carbon atoms, a phenyl group, a benzyl group, or an alkyl substituted benzyl group wherein the alkyl group has 1 to 30 carbon atoms, and X is hydroxide, bromine, chlorine, iodine, sulfate, paratoluene sulfonate or acetate.

2. A process according to claim 1 wherein the organic quaternary salt is present in an amount in the range of 0.01 to 10 weight percent based on the alkyl halide and alkyl arylsulfonate.

3. A process according to claim 1 wherein the lower alkyl arylsulfonate is methyl para-methyl benzene sulfonate, methyl para-bromo benzene sulfonate, ethylbenzene sulfonate, butyl-benzene sulfonate, propylchloro-benzene sulfonate, ethyl para-methyl benzene sulfonate, or ethyl butylbenzene sulfonate.

4. A process according to claim 1 wherein X is bromine, chlorine, hydroxy or para-toluene sulfonate.

5. The process according to claim 1 wherein M is nitrogen.

6. The process according to claim 1 wherein M is phosphorus.

7. A process for exchanging alkyl moieties between compounds which comprises reacting a lower alkyl aryl sulfonate with a higher alkyl halide at temperatures in the range of 0C to 200C in the presence of an inert solvent and at least 0.01 weight percent of an organic quaternary salt based on the total alkyl halide and alkyl aryl sulfonate; said lower alkyl aryl sulfonate being defined by the formula wherein n is zero or one; R is halogen or C to C alkyl group, and R" is a C to C alkyl group; said higher alkyl halide being defined by the formula RX wherein R is a straight or branch chain alkyl group having 6 to 40 carbon atoms and X is chlorine, bromine, or iodine; said alkyl moieties being exchanged being R and R"; said inert solvent being benzene, toluene, paraffin, ether, or chloroform; and said organic quaternary salt being defined by the formula (R R R R M) X- wherein M is a pentavalent ion of an element selected from the group consisting of nitrogen and phosphorus; each of R R R and R independently, is an alkyl group having 1 to 30 carbon atoms, a phenyl group, a benzyl group, or an alkyl substituted benzyl group wherein the alkyl group has 1 to 30 carbon atoms, and X is hydroxide, bromine, chlorine, iodine, sulfate, paratoluene sulfonate or acetate.

* III =l= 

1. A PROCESS FOR EXCHANGING ALKYL MOIETIES BETWEEN CMPOUNDS WHICH COMPRISES REACTING A LOWER ALKYL ARYL SULFONATE WITH HIGHER ALKYL HALIDE AT TEMPERATURE IN THE RANGE OF 0*C TO 200$C IN THE PRESENCE OF AT LEAST 0.01 WEIGHT PERCENT OF AN ORGANIC QUATERNARY SALT BASED ON THE TOTAL ALKYL HALIDE AND ALKYL ARYL SULFONATE, SAID LOWER ALKYL ARYL SULFONATE BEING DEFNED BY THE FORMULA
 2. A process according to claim 1 wherein the organic quaternary salt is present in an amount in the range of 0.01 to 10 weight percent based on the alkyl halide and alkyl arylsulfonate.
 3. A process according to claim 1 wherein the lower alkyl arylsulfonate is methyl para-methyl benzene sulfonate, methyl para-bromo benzene sulfonate, ethyl-benzene sulfonate, butyl-benzene sulfonate, propyl-chloro-benzene sulfonate, ethyl para-methyl benzene sulfonate, or ethyl butylbenzene sulfonate.
 4. A process according to claim 1 wherein X is bromine, chlorine, hydroxy or para-toluene sulfonate.
 5. The process according to claim 1 wherein M is nitrogen.
 6. The process according to claim 1 wherein M is phosphorus.
 7. A process for exchanging alkyl moieties between compounds which comprises reacting a lower alkyl aryl sulfonate with a higher alkyl halide at temperatures in the range of 0*C to 200*C in the presence of an inert solvent and at least 0.01 weight percent of an organic quaternary salt based on the total alkyl halide and alkyl aryl sulfonate; said lower alkyl aryl sulfonate being defined by the formula 